WO2021053953A1 - Dispersion, composition d'encre et article imprimé - Google Patents

Dispersion, composition d'encre et article imprimé Download PDF

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Publication number
WO2021053953A1
WO2021053953A1 PCT/JP2020/027732 JP2020027732W WO2021053953A1 WO 2021053953 A1 WO2021053953 A1 WO 2021053953A1 JP 2020027732 W JP2020027732 W JP 2020027732W WO 2021053953 A1 WO2021053953 A1 WO 2021053953A1
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Prior art keywords
ink composition
acrylate
dispersion
meth
base material
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PCT/JP2020/027732
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English (en)
Japanese (ja)
Inventor
欣 閔
祐子 増山
佐藤　潤
政人 岡田
史泰 村上
山崎　史絵
優子 藤岡
Original Assignee
株式会社Ｄｎｐファインケミカル
大日本印刷株式会社
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Priority to EP20864374.2A priority Critical patent/EP4032959A4/fr
Priority to JP2021504548A priority patent/JP6950115B2/ja
Publication of WO2021053953A1 publication Critical patent/WO2021053953A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents

Definitions

  • the present invention relates to dispersions, ink compositions, and printed matter.
  • Patent Documents 1 to 5 describe techniques relating to an ink composition dissolved in a fluorescent dye.
  • these ink compositions are prepared by dissolving a fluorescent dye, the dissolved dye has a problem that it has weak light resistance, heat resistance, chemical resistance and the like.
  • Patent Documents 6 to 8 describe techniques relating to an ink composition containing a resin colored with a fluorescent dye.
  • these ink compositions use a dye (fluorescent dye) as a phosphor, and have a problem that they are very weak in light resistance and chemical resistance.
  • the inkjet method is a printing method that can freely change the printing pattern because it does not require a plate and can support digital printing. Since such an inkjet method can freely change the print pattern, it is particularly useful as an ink composition for producing a printed matter that requires security.
  • the ink composition ejected by the inkjet method is ejected from the inkjet nozzle, ejection stability is required.
  • the fluorescent dye in the dissolved state is decomposed in the ink composition to lose the light emitting property, and the components contained in the ink composition are precipitated and ejected. Stability was sometimes reduced.
  • the light emission may disappear due to changes in the physical or chemical environment around the metal element.
  • a phosphor dissolved in a solvent water or an organic solvent
  • the light emitting mechanism may not function, and the light emitted by the phosphor may disappear. It became clear by their research.
  • the present invention is a dispersion capable of producing an ink composition having high ejection stability while suppressing loss of luminescence of a phosphor even in a dispersion liquid used for an ink composition ejected by an inkjet method.
  • the purpose is to provide the liquid.
  • the present inventors have found that the above problems can be solved if the dispersion liquid in which the fluorescent light emitting complex containing a rare earth metal element is dispersed in the dispersion liquid.
  • the present invention has been completed. Specifically, the present invention provides the following.
  • An ink composition ejected by an inkjet method An ink composition in which a fluorescent light-emitting complex containing a rare earth metal element is dispersed in the ink composition.
  • An overcoat layer is provided on the surface of the print layer, and the total light transmittance of the overcoat layer measured based on JIS K7361-1 is 50% or more (7) to (10). Printed matter described in either.
  • the present invention even if it is a dispersion liquid used for an ink composition ejected by an inkjet method, it is possible to suppress loss of luminescent property of a phosphor and to produce an ink composition having high ejection stability. It is a dispersion that can be used.
  • the dispersion liquid according to the present embodiment is a dispersion liquid in which a fluorescent light emitting complex containing a rare earth metal element is dispersed in the dispersion liquid.
  • Dispersion is a state in which the solute is suspended in the dispersion liquid, unlike the dissolution in which the solute is uniformly mixed in the solvent.
  • the median diameter D50 of the fluorescent light-emitting complex is in a state of a predetermined value or more, for example, 0.01 ⁇ m or more.
  • the dispersion medium for dispersing the fluorescent light-emitting complex is not particularly limited, and for example, the fluorescent light-emitting complex may be dispersed in an active energy ray-polymerizable compound that polymerizes and cures by irradiating with active energy rays. Further, it may be an organic solvent used in a solvent-type ink composition. The active energy ray-polymerizable compound and the organic solvent will be described later.
  • the fluorescent light emitting complex contained in the dispersion liquid according to the present embodiment will be described.
  • the fluorescent light emitting complex may be a dispersion medium of either an active energy ray-polymerizable compound and / or an organic solvent.
  • the fluorescent light emitting complex contains a rare earth metal element. When this fluorescent light-emitting complex absorbs light and reaches an energy-excited state, it emits light by emitting energy corresponding to the energy band gap as light.
  • a simple light source such as a black light (a light using a light source that emits ultraviolet rays) can be used as an excitation source to authenticate light emission with the human eye.
  • the ligand that coordinates the rare earth ion is selected from a phosphine oxide compound, an oxygen-containing aromatic heterocyclic compound, a nitrogen-containing aromatic heterocyclic compound, a sulfur-containing aromatic heterocyclic compound, a diketo compound, and a halogenated diketo compound. It preferably contains at least one organic ligand.
  • Examples of the phosphine oxide compound include those containing a phosphine oxide ligand represented by the following general formula (1).
  • Ar 1 and Ar 2 are monovalent aromatic groups which may independently have a substituent.
  • Ar 3 is a divalent group represented by the following general formulas (2a), (2b) and (2c), and n is 1 or 2.
  • R 1 is an independently monovalent substituent
  • X is a sulfur atom or an oxygen atom
  • R 2 is a hydrogen atom or a hydrocarbon group.
  • m is an integer from 0 to a replaceable site in the ring to which R 1 is bonded. When m is an integer of 2 or more, R 1 may be the same or different.
  • E in the formula (1) is a hydrogen atom or a phosphine oxide group represented by the following formula (3).
  • Ar 4 and Ar 5 are monovalent aromatic groups that may independently have a substituent.
  • oxygen-containing aromatic heterocyclic compound examples include compounds such as oxol, pyran, 2-pyrone, 4-pyrone, chromene, isochromen, xanthene, and oxepin.
  • Nitrogen-containing aromatic heterocyclic compounds include, for example, pyrrol, pyridine, 2-methylpyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, 2,6-rutidine, pyrimidine, pyridazine, pyrazine, oxazole, imidazole.
  • sulfur-containing aromatic heterocyclic compound examples include tris [1,1,1,5,5,5-hexafluoro-2,4-butandione 4,4,5,4-trifluoro-1- (2-thienyl). ) -1,3-Butandione], Tris [4,4,5,4-trifluoro-1- (2-thienyl) -1,3-butandione], benzothiophene, thiophene, thiepine, thiapyran, thiazole, thiazine, etc. Examples include the compound contained.
  • diketo compound examples include ⁇ -, ⁇ -, and ⁇ -diketone compounds (also referred to as dicarbonyl compounds) such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, and benzoyltrifluoroacetone.
  • rare earth metal element contained in the rare earth complex those capable of forming a complex with the above-mentioned ligand are preferable, and among them, Eu 3+ , Eu 2+ , Tb 3+ , Sm 3+ , Yb 3+ , Nd 3+ , Er 3+ , Pr 3+. , Tm 3+ , Dy 3+ , Ce 3+ , Ho 3+ , and Gd 3+, more preferably containing at least one rare earth ion selected from the group.
  • the complex include, for example, (M (CH 3 COCHCOCH 3 ) 3 (H 2 O) n , M (hfa) 3 (H 2 O) n , M (hfa) 3 (TPPO) 2 , M (btfa). ) 3 (H 2 O) n , M (btfa) 3 (TPPO) 2 , [M (hfa) 3 (dpbp)] n etc.
  • the particle size (median diameter D50) of the rare earth complex is preferably 5 ⁇ m or less. As a result, the possibility that the rare earth complex will settle can be reduced, and the ejection stability of the ink composition can be improved. Since the rare earth complex has a ligand, the dispersibility becomes good due to the interaction with the dispersant and the dispersion medium, and it is presumed that the possibility of sedimentation can be reduced. Therefore, a wide range of dispersion media can be selected for the dispersion liquid according to the present embodiment.
  • the particle size (median diameter D50) of the rare earth complex is more preferably 3 ⁇ m or less, and further preferably 1 ⁇ m or less.
  • the median diameter D50 of the rare earth complex is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
  • the particle size (median diameter D50) of the rare earth complex can be measured by, for example, Microtrack Bell Co., Ltd. "Microtrack”, Otsuka Electronics "FPAR”, HORIBA “Partica”, or the like.
  • the content of the fluorescent light-emitting complex in the dispersion is not particularly limited as long as it can be dispersed in the dispersion, and is preferably 1.0% by mass or more in the total amount of the dispersion, for example, 10.0% by mass. More preferably, it is more preferably 15.0% by mass or more.
  • the content of the dispersant is preferably 40.0% by mass or less, more preferably 35.0% by mass or less, and most preferably 30.0% by mass or less in the total amount of the dispersion liquid.
  • Dispersant examples include Kawaken Fine Chemicals "Hinoact”, Big Chemie “DISPERBYK”, “BYK”, “BYKJET”, Kusumoto Kasei “Disparon”, Lubrizol “SOLSPERSE”, “SOLPLUS”, BASF "Discex”, “EFKA”. , Ajinomoto Fine Techno “Ajispar” and the like.
  • a dispersant containing a basic group is preferable. Since the fluorescence-emitting complex containing a rare earth metal element has a high affinity with the particle surface and a high dispersion effect, it becomes easier to control the particle size of the fluorescence-emitting complex.
  • the particle surface of the fluorescent light-emitting complex containing a rare earth metal element is Lewis-acidic, it acts as a Lewis base in addition to the amine-based compound generally used as a basic group in the above-mentioned dispersant.
  • Compounds that can be used as a dispersant can also be used.
  • a carbonyl group, a carboxylic acid group, an aromatic compound, and a silicon compound can act as a Lewis base, which makes it easier to control the particle size of the fluorescent light-emitting complex, which is preferable.
  • the content of the dispersant in the dispersion liquid may not be (0% by mass) as long as the fluorescent light emitting complex can be dispersed in the dispersion liquid.
  • the amount is not particularly limited as long as the amount of the fluorescent light emitting complex can be dispersed in the dispersion liquid.
  • the content of the dispersant is preferably 20.0% by mass or less, and more preferably 15.0% by mass or less, based on the total amount of the dispersion liquid.
  • Dispersion solution containing active energy ray-polymerizable compound contains an active energy ray-polymerizable compound.
  • Active energy ray-polymerizable compounds are obtained by irradiating electromagnetic waves such as far-ultraviolet rays, ultraviolet rays, near-ultraviolet rays, visible rays, infrared rays, X-rays, and ⁇ -rays, as well as active energy rays of electron beams, proton rays, and neutron rays. It is a compound having an ethylenically unsaturated double bond to be polymerized.
  • active energy ray-polymerizable compound As the active energy ray-polymerizable compound, a radical polymerizable compound, a cationically polymerizable compound, an unsaturated group-containing compound and the like can be used without particular limitation. As the active energy ray-polymerizable compound, it is preferable to use an unsaturated group-containing compound, and as the unsaturated group-containing compound, for example, a monofunctional polymerizable compound having one ethylenically unsaturated double bond and a monofunctional polymerizable compound. / Or a polyfunctional polymerizable compound having two or more ethylenically unsaturated double bonds can be mentioned.
  • Examples of the active energy ray-polymerizable compound include (meth) acrylic acid-based compounds; maleic acid-based compounds; urethane-based, epoxy-based, polyester-based, polyol-based, and vegetable oil-based compounds modified with ethylenically unsaturated double bonds. Examples thereof include compounds having. From the viewpoint of discharge stability, it is preferable to contain a (meth) acrylic acid group-containing compound ((meth) acrylate). In addition, in this specification, "(meth) acrylate” means both acrylate and methacrylate.
  • Examples of the monofunctional (meth) acrylate include phenoxyethyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate.
  • bifunctional (meth) acrylate examples include 1,6-hexyldi (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth).
  • the content of the active energy ray-polymerizable compound in the dispersion is not particularly limited as long as it can disperse the fluorescent light-emitting complex, and is preferably 50.0% by mass or more in the total amount of the dispersion, for example, 55.0. More preferably, it is by mass% or more.
  • the content of the active energy ray-polymerizable compound is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, based on the total amount of the dispersion liquid.
  • the dispersion liquid according to the present embodiment may further contain other components, if necessary, as long as the effects of the present disclosure are not impaired.
  • other components include polymerization inhibitors, antioxidants, solvents, pigments, surfactants, and the like.
  • the solvent an organic solvent described later can be used.
  • the organic solvent is one in which the fluorescent light emitting complex can be dispersed in the dispersion liquid.
  • the organic solvent can be used as long as it is an organic solvent in which dissolution, decomposition, and ligand exchange of the fluorescent light-emitting complex are not promoted.
  • any solvent having a molecular weight of 50 or more or a boiling point of 60 ° C. or more can be used, and there is little risk of eliminating fluorescence emission due to dissolution, decomposition, or ligand exchange of the complex, and there is little risk of disappearing. It becomes easy to obtain the required performance as an ink jet ink composition.
  • organic solvent examples include alkyl alcohols having 3 to 5 carbon atoms such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, and n-pentanol; Monohydric alcohols such as -methoxy-3-methyl-1-butanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, 3-methoxy-n-butanol; 1-dimethylformamide, dimethylacetamide, 3-methoxypropanamide, 3-butoxypropaneamide, N, N-dimethyl-3-methoxypropanamide, N, N-dibutyl-3-methoxypropanamide, N, N-dibutyl-3-butoxypropaneamide, N, Amidos such as N-dimethyl-3-butoxypropanamide; Ketones or ketoalcohols such as acetone and diacetone alcohols; Ether
  • Alkyl ethers ethyl diglycol acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl Dialkyl ethers of polyhydric alcohols such as ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether; monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, Alkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine and N-butyldiethanolamine; nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, 2-pyrrol
  • the content of the organic solvent in the dispersion liquid is not particularly limited as long as it can disperse the fluorescent light emitting complex containing a rare earth metal element, and is preferably 50.0% by mass or more in the total amount of the dispersion liquid, for example. More preferably, it is 60.0% by mass or more. Further, it is preferably 95.0% by mass or less, and more preferably 90.0% by mass or less in the total amount of the dispersion liquid.
  • the dispersion liquid according to the present embodiment may further contain other components, if necessary, as long as the effects of the present disclosure are not impaired.
  • other components include antioxidants, pigments, resins, surfactants, defoamers, and the like.
  • the dispersion can be produced, for example, by dispersing each component using a paint shaker.
  • the particle size (median diameter D50) of the fluorescent light-emitting complex can be controlled by dispersion conditions such as dispersion time.
  • a fluorescent light emitting complex containing a rare earth metal element is dispersed in the ink composition.
  • the fluorescent light emitting complex By dispersing the fluorescent light emitting complex in the ink composition in this way, it is possible to suppress the loss of the light emitting property of the phosphor (fluorescent light emitting complex) and improve the ejection stability of the ink composition. ..
  • the ink composition ejected by the inkjet method according to the present embodiment has excellent ejection properties and storage stability, and further has good luminescence and excellent durability, so that the ink composition has excellent designability and durability. Suitable for printed matter with excellent security.
  • This ink composition can be produced by the dispersion liquid according to the above embodiment. Further, even if the ink composition according to the present embodiment is produced by directly dispersing the fluorescent light emitting complex containing a rare earth metal element and containing each component without using the dispersion liquid according to the above embodiment. Good.
  • the content of the fluorescent light emitting complex in the ink composition is not particularly limited as long as it is an amount that can form an information pattern that can authenticate the light emission with the human eye by irradiating with a predetermined ultraviolet ray.
  • it is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more in the total amount of the ink composition.
  • the content of the fluorescent light-emitting complex is preferably 30.0% by mass or less, and more preferably 25.0% by mass or less, based on the total amount of the ink composition.
  • the content of the dispersant in the ink composition may not be (0% by mass) as long as the fluorescent light emitting complex can be dispersed in the ink composition.
  • the amount is not particularly limited as long as the amount of the fluorescent light emitting complex can be dispersed in the dispersion liquid. More preferred.
  • the content of the dispersant is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, based on the total amount of the ink composition.
  • an active energy curable ink composition can be produced by containing a dispersion liquid containing an active energy ray-polymerizable compound and a polymerization initiator.
  • a solvent ink composition may be obtained by containing a dispersion liquid containing an organic solvent, a solvent and a resin.
  • water may be contained in the water-based ink composition.
  • an active energy curable ink composition there are few volatile components, it is excellent in environmental safety, and the printed matter obtained by curing with active energy rays can be post-processed immediately after printing, and is excellent in workability. It also has the advantage of being able to print on a wide range of substrates.
  • the content of the active energy ray-polymerizable compound in the active energy curable ink composition is not particularly limited as long as it is an amount capable of dispersing the fluorescent light emitting complex and capable of forming an appropriate cured film.
  • it is preferably 50.0% by mass or more, and more preferably 55.0% by mass or more, based on the total amount of the ink composition.
  • the content of the active energy ray-polymerizable compound is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, based on the total amount of the ink composition.
  • the active energy curable ink composition may also contain a predetermined amount of an organic solvent and / or water.
  • an ink composition containing an organic solvent In the case of an ink composition containing an organic solvent, a printed matter having excellent smoothness and glossiness can be obtained, and the apparatus can be made relatively inexpensive. Therefore, in the ink composition containing an organic solvent, even if the base material is a non-absorbent base material such as a resin base material, the ink slightly permeates into the base material due to the attack property, thereby preventing falsification of the information pattern. It has the advantage of being able to do it.
  • the content of the organic solvent in the ink composition containing the organic solvent is not particularly limited as long as it can disperse the fluorescent light emitting complex containing the rare earth metal element.
  • 70.0% by mass in the total amount of the ink composition is preferably 75.0% by mass or more, and more preferably 75.0% by mass or more. Further, it is preferably 97.0% by mass or less, more preferably 95.0% by mass or less, based on the total amount of the ink composition.
  • the use of the ink composition according to the present embodiment is not particularly limited, but since it is an ink composition having high ejection stability in inkjet ejection, it is like an individual identification number (ID number) or a face photograph. It is particularly preferable to use it for printing security information that can change depending on the individual.
  • ID number individual identification number
  • face photograph a face photograph
  • the active energy ray polymerization initiator in the active energy curable ink composition is not particularly limited as long as it promotes the polymerization reaction of a compound having an ethylenically unsaturated double bond by irradiation with active energy rays.
  • a known active energy ray polymerization initiator can be used.
  • Specific examples of the active energy ray polymerization initiator include aromatic ketones including thioxanthone, ⁇ -aminoalkylphenones, ⁇ -hydroxyketones, acylphosphine oxides, aromatic onium salts, and organic peroxides.
  • the content of the active energy ray polymerization initiator in the active energy curable ink composition may be an amount that can appropriately initiate the polymerization reaction of the active energy ray-polymerizable compound, and is 1.0% by mass in the total amount of the ink composition.
  • the above is preferable, and 3.0% by mass or more is more preferable. Further, it is preferably 20.0% by mass or less in the total amount of the ink composition.
  • the active energy ray polymerization initiator is not always essential. For example, when an electron beam is used as the active energy ray, the active energy ray polymerization initiator may not be used. ..
  • the binder resin can improve the fixability and water resistance of the ink composition.
  • the binder resin is not particularly limited, and for example, acrylic resin, polystyrene resin, polyester resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride copolymer resin, polyethylene resin, urethane resin, rosin-modified resin, phenyl resin, etc.
  • Terpen resin polyamide resin, vinyl toluene- ⁇ -methylstyrene copolymer, ethylene-vinyl acetate copolymer, cellulose acetate butyrate, silicone (silicon) resin, acrylamide resin, epoxy resin, or copolymer resin thereof. Or a mixture can be used.
  • the content of the binder resin is not particularly limited, and is preferably 0.3% by mass or more, more preferably 1.0% by mass or more, based on the total amount of the ink composition. Further, it is preferably 15.0% by mass or less, and more preferably 10.0% by mass or less in the total amount of the ink composition.
  • the binder resin may contain either an active energy curable ink composition or an ink composition containing an organic solvent.
  • the printed matter is a laminate in which the printed layer of the ink composition is formed on the surface of the base material.
  • Printed materials include, for example, bills, checks, stock certificates, corporate bonds, securities such as various securities, bank tickets, gift certificates, transportation tickets, admission tickets for facilities and events, lottery tickets, and voting tickets for public competitions. Examples include tickets, stamps, credit cards and other cards, IC cards, my number certificates, passports, identification cards, various commercial printed materials, posters and the like.
  • the ink composition according to the present embodiment is characterized in that it is ejected by an inkjet method. Since personal information such as an identification number (ID number) and a face photograph is information that changes depending on the individual, it is preferable to print by an inkjet method in which the printing pattern can be freely changed.
  • ID number an identification number
  • face photograph is information that changes depending on the individual
  • FIG. 1 shows an example of printed matter.
  • the printed matter 1 of FIG. 1 is an identification card, and an information pattern 12 so-called personal information such as an individual identification number (ID number) and a face photograph is printed with a normal ink composition.
  • An information pattern 11 similar to the information pattern 12 is printed on the printed matter 1 with the ink composition according to the present embodiment.
  • the information pattern 11 cannot be visually recognized in an environment under normal visible light, it can be visually recognized by irradiating the surface of the printed matter 1 with the light emitted from the black light a.
  • the authenticity can be determined by collating the information pattern 11 printed by the ink composition according to the present embodiment with the information pattern 12.
  • the information pattern 12 is not limited to personal information, and may be a printed pattern.
  • FIG. 2 is a cross-sectional view taken along the line XX of FIG.
  • the printing layer 11 of the ink composition according to the present embodiment in which the fluorescent light emitting complex is dispersed is formed (printed) on a part of the surface of the base material 13 together with the printing layer 12. Both sides of the base material 13 are sandwiched by the overcoat layers 14 and 15.
  • the overcoat layer is a layer that protects the surface of the printed matter, and is, for example, a layer formed by applying a conventionally known overcoat agent.
  • the overcoat layer is not essential to provide the overcoat layer in the printed matter according to the present embodiment, but in particular, by providing the overcoat layer 14 on the laminated side of the print layers 11 and 12, the print layer (information pattern) is protected from scratches and the like. This makes it possible to prevent falsification of the information pattern of the print layer. From the viewpoint of improving the visibility of the information patterns 11 and 12, it is preferable that the overcoat layer can transmit light. In that case, the total light transmittance of the overcoat layer measured based on JIS K 7361-1 is 50. % Or more is preferable.
  • the color of the base material 13 and / or the color of the information pattern 12 and the color of the information pattern 11 are the same. Under normal visible light, it becomes difficult to visually discriminate the information pattern 11 printed by the ink composition according to the present embodiment, and a printed matter having higher security can be obtained.
  • the color and / or information pattern 12 of the printing layer other than the information pattern 12 and the information pattern 11 It is preferable that the color is the same.
  • the printing layer other than the information pattern 12 and the information pattern 12 may be ejected (printed) by an inkjet method using a normal ink composition, but even in offset printing, gravure printing, flexo printing, etc., a laser beam is applied by laser light irradiation.
  • the print layer may be formed in the form of a laser color-developing layer as printed by.
  • the information pattern 11 in the printed matter 1 of FIGS. 1 and 2 is printed so as not to overlap with the information pattern 12, but is printed by the information pattern printed by the ink composition according to the present embodiment and the ordinary ink composition.
  • the information patterns may be partially or wholly overlapped in the plan view of the base material. As a result, it is possible to increase the print area of the information pattern printed by the ink composition according to the present embodiment, and it is possible to irradiate the surface of the printed matter with light to emit light in a larger area. ..
  • the printed matter according to the present embodiment may be provided with other layers such as a base material layer, an adhesive layer, a primer layer, and an ultraviolet absorbing layer, if necessary.
  • base material examples include high-quality paper, art paper, coated paper, cast-coated paper, synthetic resin or emulsion-impregnated paper, synthetic rubber latex-impregnated paper, synthetic resin inner sheet paper, papers such as cellulose fiber paper, and polyolefin (polyethylene). , Polypropylene, etc.), Polystyrene, Polycarbonate, Polyethylene terephthalate, Polyvinyl chloride, Polymethacrylate and other synthetic resin plastic sheets, and opaque films or base materials formed by adding pigments and fillers to these synthetic resins. Examples thereof include a film having fine voids (microvoids) inside (so-called synthetic paper).
  • the base material does not necessarily have to be in the form of a film or a sheet, and may be a resin molded body having a three-dimensional shape or the like.
  • the base material does not contain a whitening agent so that the ink composition can be visually recognized more clearly when irradiated with black light.
  • a base material containing a whitening agent it is preferable to use an ink composition in which a fluorescent light emitting complex that does not emit blue light is dispersed.
  • an absorbent base material Since the ink composition is absorbed inside the base material, there is an advantage that falsification of the information pattern can be prevented.
  • the absorbent base material include a base material having voids in the base material such as paper.
  • the inkjet recording device that ejects the ink composition onto the surface of the base material can be applied to any of the inkjet recording devices such as the piezo method, the thermal method, and the electrostatic method.
  • the ink composition is an active energy ray-curable ink composition
  • the ink composition ejected onto the surface of the base material is irradiated with active energy rays.
  • the active energy ray include electromagnetic waves such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, visible rays, infrared rays, X-rays, and ⁇ rays, as well as active energy rays of electron beams, proton rays, and neutron rays.
  • the light source for irradiating the active energy ray is not particularly limited, and examples thereof include a high-pressure mercury lamp, a metal halide lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ultraviolet laser, sunlight, and an LED lamp. It is more preferable to use an LED lamp as a light source from the viewpoint of energy saving and a high degree of freedom in the design equipment of the printing apparatus.
  • the ink composition is a solvent-type ink composition
  • the ink composition ejected onto the surface of the base material is dried.
  • the drying conditions are appropriately set depending on the boiling point of the solvent contained in the ink composition.
  • fluorescent substance A is Central Techno Co., Ltd. Lumisys E-300 (Eu (hfa) 3 (TPPO) 2 (Tris [1,1,1,5,5,5-hexafluoro-2, 4-Butandionato] bis (triphenylphosphine oxide) europium (III) complex)).
  • the phosphor A is a fluorescent light emitting complex containing a rare earth metal element.
  • polymer B includes tris [1,1,1,5,5,5-hexafluoro-2,4-butandionato] europium (III) and biphenyl-4,4'-diylbis (diphenyl). It is a complex polymer composed of phosphine oxide).
  • the phosphor B is a fluorescent light-emitting complex containing a rare earth metal element. It was manufactured with reference to known documents such as Japanese Patent No. 4407224 and Japanese Patent No. 5904600.
  • polymer C includes tris [4,5,4,4-trifluoro-1- (2-thienyl) -1,3-butandionato] europium (III) and biphenyl-4,4'-. It is a complex polymer composed of diylbis (diphenylphosphine oxide).
  • the phosphor C is a fluorescent light-emitting complex containing a rare earth metal element. It was manufactured with reference to known documents such as Japanese Patent No. 4407224 and Japanese Patent No. 5904600.
  • polymer D includes tris [1,1,1,5,5,5-hexafluoro-2,4-butandionato] terbium (III) and biphenyl-4,4'-diylbis (diphenyl). It is a complex polymer composed of phosphine oxide).
  • the phosphor D is a fluorescent light emitting complex containing a rare earth metal element. It was manufactured with reference to known documents such as Japanese Patent No. 4407224 and Japanese Patent No. 5904600.
  • fluorescent body E is GOF-SS (ZnO: O), a fluorescent material manufactured by Nemoto Lumimaterial Co., Ltd.
  • the phosphor E is an inorganic phosphor, not a fluorescent light-emitting complex containing a rare earth metal element.
  • fluorescent body F is rhodamine B, which is a red luminescent organic dye.
  • the "resin” (binder resin) is "Paraloid B60” manufactured by Dow Inc., which is an acrylic resin.
  • the "polymerization initiator” is "Omnirad TPO" manufactured by IGM Resins BV.
  • the "surfactant” is "BYK-UV 3500” manufactured by Big Chemie.
  • the light resistance of the ink compositions of Examples and Comparative Examples was tested. Specifically, the ink composition was ejected onto the surface of the base material by an inkjet method to produce a printed matter having a printed layer formed on the surface of the base material. Then, using a xenon lamp (Ci4000 weather meter manufactured by Atlas, inner filter: quartz, outer filter: soda lime & infrared absorption coating (CIRA)), the illuminance is 1.2 mW / m 2 , and the light is emitted before and after the irradiation test for 50 hours. The condition was visually evaluated.
  • a xenon lamp Ci4000 weather meter manufactured by Atlas, inner filter: quartz, outer filter: soda lime & infrared absorption coating (CIRA)
  • the ink composition of the example in which the fluorescent light emitting complex is dispersed suppresses the loss of the light emitting property of the phosphor and produces an ink composition having high ejection stability. You can see that you can.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne une dispersion qui, même lorsqu'elle est utilisée dans une composition d'encre pour éjection par l'intermédiaire d'un procédé à jet d'encre, empêche la perte de luminescence de luminophore et permet la fabrication d'une composition d'encre ayant une stabilité d'éjection élevée.　La dispersion est utilisée dans une composition d'encre pour éjection par l'intermédiaire d'un procédé à jet d'encre, et un complexe fluorescent contenant un élément de métal des terres rares est dispersé dans la dispersion. Le diamètre médian D50 du complexe fluorescent est de préférence inférieur ou égal à 5 µm.
PCT/JP2020/027732 2019-09-19 2020-07-16 Dispersion, composition d'encre et article imprimé WO2021053953A1 (fr)

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EP20864374.2A EP4032959A4 (fr) 2019-09-19 2020-07-16 Dispersion, composition d'encre et article imprimé
JP2021504548A JP6950115B2 (ja) 2019-09-19 2020-07-16 分散液、インク組成物、及び印刷物

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JP2019170894 2019-09-19
JP2019-170894 2019-09-19

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JPS594600B2 (ja) 1976-07-02 1984-01-30 三井液化ガス株式会社 低温液化ガスタンク
JPH10250214A (ja) * 1997-03-11 1998-09-22 Dainippon Printing Co Ltd 蛍光画像形成物
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JP4407224B2 (ja) 2003-10-06 2010-02-03 Ｄｉｃ株式会社 印刷インキおよび印刷物
JP2010215686A (ja) 2009-03-13 2010-09-30 National Institute Of Advanced Industrial Science & Technology 希土類金属錯体及びその製造方法並びにそれを用いた希土類金属錯体組成物。
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JP2018095750A (ja) 2016-12-14 2018-06-21 大日本塗料株式会社 インクジェットインク組成物、インクジェットインクセット、蛍光検出方法、蛍光検出センサー、及び対象物の識別方法
JP2019056111A (ja) 2018-09-28 2019-04-11 大日本塗料株式会社 インクジェットインク組成物、インクジェットインクセット、蛍光検出方法、蛍光検出センサー、及び対象物の識別方法

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CN1890110A (zh) * 2003-12-11 2007-01-03 佳能株式会社 图像、记录方法、信息识别方法和信息识别系统
JP5574755B2 (ja) * 2010-02-26 2014-08-20 大日本塗料株式会社 無機蛍光体分散液の製造方法、無機蛍光体分散液を有するコーティング組成物及びインクジェット用インク
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS594600B2 (ja) 1976-07-02 1984-01-30 三井液化ガス株式会社 低温液化ガスタンク
JPH10250214A (ja) * 1997-03-11 1998-09-22 Dainippon Printing Co Ltd 蛍光画像形成物
JP2002188026A (ja) * 2000-10-11 2002-07-05 Hitachi Maxell Ltd 水性蛍光インク組成物
JP2003261804A (ja) 2002-03-12 2003-09-19 Nippon Kayaku Co Ltd インク組成物
JP2004027155A (ja) * 2002-06-28 2004-01-29 Dainippon Ink & Chem Inc 希土類蛍光錯体の水性分散体の製造方法および水性記録液の製造方法
JP4407224B2 (ja) 2003-10-06 2010-02-03 Ｄｉｃ株式会社 印刷インキおよび印刷物
JP2008291167A (ja) * 2007-05-28 2008-12-04 Toyo Ink Mfg Co Ltd 平版インキ組成物
JP2008303196A (ja) 2007-06-11 2008-12-18 Orient Chem Ind Ltd β−ジケトン希土類金属錯体、その製造方法および製造中間体、ならびにβ−ジケトン希土類金属錯体を含むインキ組成物
JP2010215686A (ja) 2009-03-13 2010-09-30 National Institute Of Advanced Industrial Science & Technology 希土類金属錯体及びその製造方法並びにそれを用いた希土類金属錯体組成物。
JP2013241565A (ja) 2012-02-01 2013-12-05 Mimaki Engineering Co Ltd インク及びその利用
JP2014047227A (ja) 2012-08-29 2014-03-17 General Co Ltd 非水性インクジェットインク
WO2014129416A1 (fr) * 2013-02-19 2014-08-28 国立大学法人奈良先端科学技術大学院大学 Jeu d'encres, matière imprimée et procédé d'impression
JP2016035047A (ja) 2014-08-04 2016-03-17 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ 封入された蛍光染料およびフォトクロミック染料のポリウレタン分散物
JP2018095750A (ja) 2016-12-14 2018-06-21 大日本塗料株式会社 インクジェットインク組成物、インクジェットインクセット、蛍光検出方法、蛍光検出センサー、及び対象物の識別方法
JP2019056111A (ja) 2018-09-28 2019-04-11 大日本塗料株式会社 インクジェットインク組成物、インクジェットインクセット、蛍光検出方法、蛍光検出センサー、及び対象物の識別方法

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EP4032959A4 (fr) 2023-10-25
JP6950115B2 (ja) 2021-10-13
JPWO2021053953A1 (ja) 2021-09-30

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